CN109715693B - Polymerizable composition for optical material, optical material obtained from the composition, and method for producing the same - Google Patents

Polymerizable composition for optical material, optical material obtained from the composition, and method for producing the same Download PDF

Info

Publication number
CN109715693B
CN109715693B CN201780056510.2A CN201780056510A CN109715693B CN 109715693 B CN109715693 B CN 109715693B CN 201780056510 A CN201780056510 A CN 201780056510A CN 109715693 B CN109715693 B CN 109715693B
Authority
CN
China
Prior art keywords
compound
bis
weight
parts
polymerizable composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201780056510.2A
Other languages
Chinese (zh)
Other versions
CN109715693A (en
Inventor
龙昭宪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Original Assignee
Mitsui Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Publication of CN109715693A publication Critical patent/CN109715693A/en
Application granted granted Critical
Publication of CN109715693B publication Critical patent/CN109715693B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0073—Optical laminates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/12—Polarisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00432—Auxiliary operations, e.g. machines for filling the moulds
    • B29D11/00442—Curing the lens material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

The present invention provides a polymerizable composition for optical materials, which comprises: (A) at least 1 amine compound selected from the group consisting of the compound (a1) represented by the general formula (1) and the compound (a2) represented by the general formula (2), (B) an isocyanate (thio) cyanate compound having 2 or more isocyanate groups, and (C) a polythiol compound comprising a dithiol compound (C1) having 2 mercapto groups and a polythiol compound (C2) having 3 or more mercapto groups.

Description

Polymerizable composition for optical material, optical material obtained from the composition, and method for producing the same
Technical Field
The present invention relates to a polymerizable composition for an optical material, an optical material obtained from the composition, and a method for producing the same. More specifically, the present invention relates to a polymerizable composition for an optical material, which can give a molded body of a thiourea resin, and a method for producing the same.
Background
Plastic lenses are lighter, less likely to break, and dyeable than inorganic lenses, and therefore have rapidly become popular as optical materials for spectacle lenses, camera lenses, and the like in recent years.
The material usable as an optical material has been mainly glass since old, but in recent years, various plastics for optical materials have been developed and widely used as a substitute for glass. Plastic materials such as acrylic resins, aliphatic carbonate resins, polycarbonates, polythiourethanes and the like have been mainly used as materials for spectacle lenses and the like, because of their excellent optical properties, light weight, no cracking and excellent moldability. Among them, a representative example having a high refractive index is a polythiourethane resin obtained from a polymerizable composition containing an isocyanate compound and a thiol compound (patent document 1).
In recent years, due to changes in lifestyle, there have been increasing numbers of people who enjoy physical activities such as sports with sunglasses. Further, due to the increase in safety consciousness, there is a demand for a hard-to-break loud call for glasses for children. In view of such circumstances, there is an increasing demand for lighter and more impact-resistant substrates. In response to the increase in the demand, a urethane urea resin, which is a base material having good impact resistance, has been developed for use in spectacle lenses (patent documents 2 to 7). Further, as a lens material which achieves both impact resistance and a high refractive index, thiourethane urea resins containing an amine compound, an isocyanate compound and a thiol compound have been proposed (patent documents 8 to 12), and as a lens material having impact resistance and chemical resistance, urethane resins containing an amine compound, an isocyanate compound and a polyol compound have been proposed (patent documents 13 to 14).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 60-199016
Patent document 2: international publication No. 1996/023827
Patent document 3: international publication No. 2001/036507
Patent document 4: international publication No. 2001/036508
Patent document 5: international publication No. 2007/097798
Patent document 6: international publication No. 2009/088456
Patent document 7: international publication No. 2015/088502
Patent document 8: japanese patent laid-open publication No. 2015-003945
Patent document 9: international publication No. 2016/006605
Patent document 10: international publication No. 2016/006606
Patent document 11: japanese Kokai publication No. 2009-524725
Patent document 12: japanese Kokai publication 2017-502119
Patent document 13: japanese Kohyo publication 2011-508822
Patent document 14: japanese Kokai publication No. 2016-507626
Disclosure of Invention
Problems to be solved by the invention
A plastic lens having a high refractive index can be obtained from a thiourethane resin. However, the higher the refractive index is, the higher the specific gravity tends to be, and the more the resin having a high refractive index is, the smaller the effect on weight reduction is in some cases.
On the other hand, a urethane urea resin is a lightweight material because of its low specific gravity as compared with a thiourethane resin, and a plastic lens having good impact resistance can be obtained. However, the molded product of a urethane urea resin may have low solvent resistance and heat resistance and low light resistance, and may be colored yellow when used for a long period of time. Further, since the time from the preparation of the composition to the injection into the casting mold (hereinafter referred to as pot life) is short, the polymerization may be unevenly caused or the polymerization may be vigorously carried out in the process of the injection into the casting mold. As a result, cloudiness and striae may occur in the obtained lens.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by using 2 kinds of compounds including a dithiol compound having 2 mercapto groups and a polythiol compound having 3 or more mercapto groups in combination as the polythiol compound, and have completed the present invention.
That is, the present invention can be as follows.
[1] A polymerizable composition for optical materials, comprising:
(A) at least 1 amine compound selected from the group consisting of the compound (a1) represented by the general formula (1) and the compound (a2) represented by the general formula (2),
(B) an isocyanate (thio) cyanate compound having 2 or more isocyanate (thio) groups, and
(C) a polythiol compound comprising a dithiol compound (c1) having 2 mercapto groups and a polythiol compound (c2) having 3 or more mercapto groups.
[ chemical formula 1]
Figure BDA0001994707060000031
(in the general formula (1), R3～R5Each represents a hydrogen atom or a methyl group. p represents an integer of 0 to 100, q represents an integer of 0 to 100, r represents an integer of 1 to 100, and p + r satisfies an integer of 1 to 100. There are a plurality of R4Each other or R5May be the same or different from each other. )
[ chemical formula 2]
Figure BDA0001994707060000032
(in the general formula (2), R6、R8、R9Each represents a hydrogen atom or a methyl group. R7Represents a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms or a cyclic alkyl group having 3 to 20 carbon atoms. x + y + z represents an integer of 1 to 200. n represents an integer of 0 to 10. There are a plurality of R6Each other, R8Each other or R9May be the same or different from each other. )
[2] The polymerizable composition for optical materials according to [1], further comprising a polyol compound (D) having 2 or more hydroxyl groups.
[3] The polymerizable composition for optical materials according to [1] or [2], wherein the ratio (c1/c2) of the molar number c1 of mercapto groups of the polythiol compound (c1) to the molar number c2 of mercapto groups of the polythiol compound (c2) is in the range of 1 to 13.
[4] The polymerizable composition for optical materials according to any one of [1] to [3], wherein the ratio (a/B) of the number of moles a of amino groups of the amine compound (A) to the number of moles B of isocyanate groups of the iso (thio) cyanate compound (B) is in the range of 0.01 to 0.20.
[5] The polymerizable composition for optical materials as described in any one of [1] to [4], wherein the compound (a1) represented by the general formula (1) has a weight average Molecular Weight (MW) of 200 to 4000.
[6] The polymerizable composition for optical materials as described in any one of [1] to [5], wherein the compound (a2) represented by the general formula (2) has a weight average Molecular Weight (MW) of 400 to 5000.
[7] The polymerizable composition for optical materials according to any one of [1] to [6], wherein the dithiol compound (c1) is at least 1 selected from the group consisting of 2, 5-dimercaptomethyl-1, 4-dithiane, ethylene glycol bis (3-mercaptopropionate), 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithetane and bis (2-mercaptoethyl) sulfide,
the polythiol compound (c2) is selected from trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, at least 1 member of the group consisting of 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, and 1,1,3, 3-tetrakis (mercaptomethylthio) propane.
[8] The polymerizable composition for optical materials according to any one of [1] to [7], wherein the iso (thio) cyanate ester compound (B) is at least 1 selected from the group consisting of 1, 6-hexamethylene diisocyanate, 1, 5-pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4, 4 '-diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, toluene diisocyanate, benzene diisocyanate, and 4, 4' -diphenylmethane diisocyanate.
[9] The polymerizable composition for optical materials according to any one of [1] to [8], wherein the polyol compound (D) comprises a diol compound (D1) having 2 hydroxyl groups.
[10] The polymerizable composition for optical materials according to [9], wherein the diol compound (d1) contains at least 1 selected from the group consisting of a linear aliphatic diol compound, a branched aliphatic diol compound, a cyclic aliphatic diol compound, and an aromatic diol compound.
[11] The polymerizable composition for optical materials according to [9] or [10], wherein the diol compound (d1) is at least 1 selected from the group consisting of cyclohexanedimethanol, tricyclodecanedimethanol and polypropylene glycol.
[12] A molded article obtained by curing the polymerizable composition for optical materials according to any one of [1] to [11 ].
[13] An optical material formed from the molded body according to [12 ].
[14] A plastic lens comprising the molded article according to [13 ].
[15] A plastic polarized lens, comprising:
a polarizing film; and
a substrate layer formed of the molded article according to [12], wherein the substrate layer is formed on at least one surface of the polarizing film.
[16] A method for producing a polymerizable composition for optical materials, comprising the steps of:
a step (i) in which at least 1 amine compound (a) selected from the group consisting of an amine compound (a1) represented by general formula (1) and an amine compound (a2) represented by general formula (2) is reacted with an isocyanate compound (B) having 2 or more isocyanate (thio) groups to obtain a prepolymer; and
and (ii) adding and mixing a polythiol compound (C) comprising a dithiol compound (C1) having 2 mercapto groups and a polythiol compound (C2) having 3 or more mercapto groups to the prepolymer.
[ chemical formula 3]
Figure BDA0001994707060000061
(in the general formula (1), R3～R5Each represents a hydrogen atom or a methyl group. p represents an integer of 0 to 100, q represents an integer of 0 to 100, r represents an integer of 1 to 100, and p + r satisfies an integer of 1 to 100. There are a plurality of R4Each other or R5May be the same or different from each other. )
[ chemical formula 4]
Figure BDA0001994707060000062
(in the general formula (2), R6、R8、R9Each represents a hydrogen atom or a methyl group. R7Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. x + y + z represents an integer of 1 to 100. n represents an integer of 0 to 10. There are a plurality of R6Each other, R8Each other or R9May be the same or different from each other. )
[17] The method for producing a polymerizable composition for optical materials according to [16], wherein the step (ii) further comprises a step of adding and mixing a polyol compound (D) having 2 or more hydroxyl groups to the prepolymer obtained in the step (i).
[18] A method for producing an optical material, comprising the steps of:
a step of injecting the polymerizable composition for optical materials according to any one of [1] to [11] into a mold; and
and a step of polymerizing and curing the polymerizable composition for an optical material in the mold.
[19] A method for manufacturing a plastic polarized lens, comprising the steps of:
a step of fixing the polarizing film in a mold for lens casting molding in a state where at least one surface of the polarizing film is separated from the mold;
a step of injecting the polymerizable composition for optical materials according to any one of [1] to [11] into a space between the polarizing film and the mold; and
and a step of polymerizing and curing the polymerizable composition for optical materials, and laminating a base material layer formed of a cured product of the polymerizable composition for optical materials on at least one surface of the polarizing film.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymerizable composition for optical materials of the present invention can provide a thiourea resin molded product having a high refractive index, a low specific gravity, excellent transparency, heat resistance, solvent resistance, impact resistance and light resistance, and excellent balance of these properties by suppressing the occurrence of optical distortion (striae) due to a long pot life of the polymerizable composition. Such a thiourea resin can be suitably used for various optical materials requiring high transparency, particularly spectacle lenses.
Detailed Description
The polymerizable composition for optical materials of the present invention will be explained based on the following embodiments.
The polymerizable composition for optical materials of the present embodiment includes:
(A) at least 1 amine compound selected from the group consisting of the compound (a1) represented by the general formula (1) and the compound (a2) represented by the general formula (2),
(B) an isocyanate (thio) cyanate compound having 2 or more isocyanate (thio) groups, and
(C) a polythiol compound comprising a dithiol compound (c1) having 2 mercapto groups and a polythiol compound (c2) having 3 or more mercapto groups.
Hereinafter, each component used in the present embodiment will be described in detail.
[ amine Compound (A) ]
The amine compound (a) used in the polymerizable composition for optical materials of the present invention is formed from at least 1 selected from the group consisting of the compound (a1) represented by the general formula (1) and the compound (a2) represented by the general formula (2).
(Compound (a1))
[ chemical formula 5]
Figure BDA0001994707060000081
In the general formula (1), R3～R5Each represents a hydrogen atom or a methyl group. p is an integer of 0 to 100, preferably an integer of 0 to 70, and more preferably an integer of 0 to 35. q is an integer of 0 to 100, preferably an integer of 0 to 70, and more preferably an integer of 0 to 40. r is an integer of 1 to 100, preferably an integer of 1 to 70, and more preferably an integer of 1 to 35. p + r is an integer of 1 to 100, preferably an integer of 1 to 70, and more preferably an integer of 1 to 35. There are a plurality of R4Each other or R5May be the same or different from each other.
The weight average Molecular Weight (MW) of the compound (a1) represented by the general formula (1) may be 100 to 4000, preferably 200 to 4000, more preferably 400 to 2000, and still more preferably 500 to 2000. The compound (a1) having a weight average molecular weight within the above range is preferable because the reactivity with iso (thio) cyanate is mild, and a uniform prepolymer can be obtained as a result.
Examples of the compound represented by the general formula (1) include, but are not limited to, HK-511, ED-600, ED-900, ED-2003, D-230, D-400, D-2000, and D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.). They may be used alone or in the form of a mixture of 2 or more.
In the present embodiment, from the viewpoint of the effect of the present invention, it is preferable to use a compound represented by general formula (1a) in which p and q are both 0 as the compound (a 1).
[ chemical formula 6]
Figure BDA0001994707060000082
In the general formula (1a), R3、R5And R is independently from R of formula (1)3、R5And r means phaseThe same is true.
(Compound (a2))
Compound (a2) is represented by general formula (2).
[ chemical formula 7]
Figure BDA0001994707060000091
In the general formula (2), R6、R8、R9Each represents a hydrogen atom or a methyl group. R7Represents a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms or a cyclic alkyl group having 3 to 20 carbon atoms. x + y + z represents an integer of 1 to 200. n represents an integer of 0 to 10. There are a plurality of R6Each other, R8Each other or R9May be the same or different from each other.
In the present embodiment, x + y + z is an integer of usually 1 to 200, preferably 1 to 100, and more preferably 1 to 50 as the compound represented by the general formula (2). n is an integer of usually 0 to 10, preferably 0 to 5, and more preferably 0 or 1. The weight average Molecular Weight (MW) of the compound represented by the general formula (2) may be 100 to 5000, preferably 400 to 5000, more preferably 400 to 3000, and still more preferably 500 to 2000. The compound (a2) having a weight average molecular weight within the above range is preferable because the reactivity with iso (thio) cyanate is mild, and a uniform prepolymer can be obtained as a result.
As R7Examples of the straight-chain alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, n-octyl, nonyl, decyl, dodecyl and the like, examples of the branched alkyl group having 3 to 20 carbon atoms include isopropyl, isobutyl, tert-butyl, isopentyl, isooctyl, 2-ethylhexyl, 2-propylpentyl, isodecyl and the like, and examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
Examples of the compound represented by the general formula (2) include, but are not limited to, T-403, T-3000(XTJ-509), T-5000 (trade name, manufactured by HUNTSMAN Co., Ltd.). They may be used alone or in the form of a mixture of 2 or more.
[ iso (thio) cyanate ester Compound (B) ]
The iso (thio) cyanate compound (B) used in the polymerizable composition for optical materials of the present invention is an iso (thio) cyanate compound having 2 or more iso (thio) cyanate groups, and the iso (thio) cyanate compound refers to an isocyanate compound or an isothiocyanate compound.
Examples of the iso (thio) cyanate compound (B) include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, heterocyclic polyisocyanate compounds, aliphatic polyisothiocyanate compounds, alicyclic polyisothiocyanate compounds, aromatic polyisothiocyanate compounds, sulfur-containing heterocyclic polyisothiocyanate compounds, and modified products thereof.
More specific examples of the isocyanate compound include 1, 5-pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 4-trimethylhexane diisocyanate, 2, 4, 4-trimethyl-1, 6-hexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine triisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α, α, α ', α' -tetramethylxylylene diisocyanate, bis (isocyanatomethyl) naphthalene, mesitylene triisocyanate, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, hexamethylene diisocyanate, and the like, Aliphatic polyisocyanate compounds such as bis (isocyanatoethylthio) ethane and bis (isocyanatomethylthio) ethane;
alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4, 4' -diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 3, 8-bis (isocyanatomethyl) tricyclodecane, 3, 9-bis (isocyanatomethyl) tricyclodecane, 4, 8-bis (isocyanatomethyl) tricyclodecane and 4, 9-bis (isocyanatomethyl) tricyclodecane;
aromatic polyisocyanate compounds such as phenylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, and diphenylsulfide-4, 4-diisocyanate;
heterocyclic polyisocyanate compounds such as 2, 5-diisocyanatothiophene, 2, 5-bis (isocyanatomethyl) thiophene, 2, 5-diisocyanatotetrahydrothiophene, 2, 5-bis (isocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isocyanatomethyl) tetrahydrothiophene, 2, 5-diisocyanato-1, 4-dithiane, 2, 5-bis (isocyanatomethyl) -1, 4-dithiane, 4, 5-diisocyanato-1, 3-dithiolane, and 4, 5-bis (isocyanatomethyl) -1, 3-dithiolane; and so on. As the iso (thio) cyanate compound (B), 1 or 2 or more selected from them may be used in combination.
Further, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer-type modified compounds with polyhydric alcohols, carbodiimide-modified compounds, urea-modified compounds, biuret-modified compounds, dimerization or trimerization reaction products, and the like can also be used.
Examples of the isothiocyanate compound include aliphatic polyisothiocyanate compounds such as 1, 6-hexamethylene diisothiocyanate, lysine methyl ester diisothiocyanate, lysine triisothiocyanate, m-xylylene diisothiocyanate, bis (isothiocyanatomethyl) sulfide, bis (isothiocyanatoethyl) disulfide and the like;
alicyclic polyisothiocyanate compounds such as isophorone diisothiocyanate, bis (isothiocyanatomethyl) cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2, 5-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 3, 8-bis (isothiocyanatomethyl) tricyclodecane, 3, 9-bis (isothiocyanatomethyl) tricyclodecane, 4, 8-bis (isothiocyanatomethyl) tricyclodecane, 4, 9-bis (isothiocyanatomethyl) tricyclodecane and the like;
aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4-diphenylmethane diisothiocyanate, diphenyl disulfide-4, 4-diisothiocyanate and the like;
sulfur-containing heterocyclic polyisothiocyanate compounds such as 2, 5-diisothiocyanatothiophene, 2, 5-bis (isothiocyanatomethyl) thiophene, 2, 5-isothiocyanattetrahydrothiophene, 2, 5-bis (isothiocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isothiocyanatomethyl) tetrahydrothiophene, 2, 5-diisothiocyanato-1, 4-dithiane, 2, 5-bis (isothiocyanatomethyl) -1, 4-dithiane, 4, 5-diisothiocyanato-1, 3-dithiolane, 4, 5-bis (isothiocyanatomethyl) -1, 3-dithiolane and the like; and so on. As the iso (thio) cyanate compound (B), 1 or 2 or more selected from them may be used in combination.
Further, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer-type modified compounds with polyhydric alcohols, carbodiimide-modified compounds, urea-modified compounds, biuret-modified compounds, dimerization or trimerization reaction products, and the like can also be used.
In the present embodiment, as the iso (thio) cyanate ester compound (B), at least one selected from the group consisting of 1, 6-hexamethylene diisocyanate, 1, 5-pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4, 4 '-diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, toluene diisocyanate, benzene diisocyanate, and 4, 4' -diphenylmethane diisocyanate can be preferably used.
It is further preferable to use at least one selected from m-xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4, 4' -diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane.
[ polythiol Compound (C) ]
The polythiol compound (C) used in the polymerizable composition for an optical material of the present invention includes both a dithiol compound (C1) having 2 mercapto groups and a polythiol compound (C2) having 3 or more mercapto groups.
(dithiol Compound (c1))
The dithiol compound (c1) is a thiol having 2 mercapto groups, in other words, a di (bifunctional) thiol.
Examples of the dithiol compound (c1) include methanedithiol, 1, 2-ethanedithiol, 1, 2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1, 2-bis (2-mercaptoethylthio) ethane, 1, 2-bis (3-mercaptopropylthio) ethane, 2, 5-dimercaptomethyl-1, 4-dithiane, 2, 5-dimercapto-1, 4-dithiane, 2, 5-dimercaptomethyl-2, 5-dimethyl-1, 4-dithiane, and esters of thioglycolic acid and mercaptopropionic acid thereof;
bis (2-mercaptoethyl) sulfide, hydroxymethylsulfide bis (2-mercaptoacetate), hydroxymethylsulfide bis (3-mercaptopropionate), hydroxyethylsulfide bis (2-mercaptoacetate), hydroxyethylsulfide bis (3-mercaptopropionate), hydroxymethyldisulfide bis (2-mercaptoacetate), hydroxymethyldisulfide bis (3-mercaptopropionate), hydroxyethyldisulfide bis (2-mercaptoacetate), hydroxyethyldisulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), Aliphatic polythiol compounds such as bis (2-mercaptoethyl) dithiodipropionate and 4, 6-bis (mercaptomethylthio) -1, 3-dithiane;
aromatic polythiol compounds such as 1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 2-bis (mercaptomethyl) benzene, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 1, 2-bis (mercaptoethyl) benzene, 1, 3-bis (mercaptoethyl) benzene, 1, 4-bis (mercaptoethyl) benzene, 2, 5-methanedithiol, 3, 4-methanedithiol, 1, 5-naphthalenedithiol, and 2, 6-naphthalenedithiol;
heterocyclic polythiol compounds such as 2-methylamino-4, 6-dithiol-s-triazine, 3, 4-thiophenedithiol, 2, 5-dimercapto-1, 3, 4-thiadiazole (bismuthiol), 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, and 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiocyclobutane; and so on.
As the dithiol compound (c1), at least 1 compound selected from the group consisting of 2, 5-dimercaptomethyl-1, 4-dithiane, ethylene glycol bis (3-mercaptopropionate), 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithetane, and bis (2-mercaptoethyl) sulfide can be preferably used from the viewpoint of the effects of the present invention.
It is particularly preferable to use at least 1 compound selected from the group consisting of 2, 5-dimercaptomethyl-1, 4-dithiane, ethylene glycol bis (3-mercaptopropionate), 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, and bis (2-mercaptoethyl) sulfide.
(polythiol Compound (c2))
The polythiol compound (c2) is a polyhydric (polyfunctional) thiol having 3 or more mercapto groups, in other words, a ternary (trifunctional) or more.
Examples of the polythiol compound (c2) include 1, 2, 3-propanetrithiol, tetrakis (mercaptomethyl) methane, trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1, 2, 3-tris (mercaptomethylthio) propane, 1, 2, 3-tris (2-mercaptoethylthio) propane, 1, 2, 3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2, 3-dimercaptopropyl) sulfide, and esters of thioglycolic acid and mercaptopropionic acid thereof, esters of the same, and mixtures thereof,
Aliphatic polythiol compounds such as 1,1,3, 3-tetrakis (mercaptomethylthio) propane, 1, 2, 2-tetrakis (mercaptomethylthio) ethane, tris (mercaptomethylthio) methane, and tris (mercaptoethylthio) methane;
aromatic polythiol compounds such as 1,3, 5-trimercaptobenzene, 1,3, 5-tris (mercaptomethyl) benzene, 1,3, 5-tris (mercaptomethyleneoxy) benzene, 1,3, 5-tris (mercaptoethyleneoxy) benzene, and the like;
heterocyclic polythiol compounds such as 2, 4, 6-trimercapto-s-triazine and 2, 4, 6-trimercapto-1, 3, 5-triazine; and so on.
As the polythiol compound (c2) that can be used in the present embodiment, from the viewpoint of the effect of the present invention, a polythiol compound selected from the group consisting of trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 1,3, 3-tetrakis (mercaptomethylthio) propane.
It is particularly preferable to use at least 1 compound selected from the group consisting of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, and 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane.
In the present embodiment, the ratio (c1/c2) of the number of moles c1 of mercapto groups of the dithiol compound (c1) to the number of moles c2 of mercapto groups of the polythiol compound (c2) may be 1 to 13, preferably 1 to 11, and more preferably 1 to 9.
The number of moles of mercapto groups c1 in the dithiol compound (c1) and the number of moles of mercapto groups c2 in the polythiol compound (c2) can be calculated from the number of mercapto groups and the molecular weight of the thiol used, and the amount of thiol used. Alternatively, the molar numbers c1 and c2 can be determined by a method known in the art, such as titration.
When the molar ratio is in the above range, a thiourea resin molded product having a high refractive index can be obtained, which has a low specific gravity, is excellent in transparency, heat resistance, solvent resistance, impact resistance and light resistance, and is excellent in balance of optical distortion (striae) because of a long pot life of the polymerizable composition.
[ polyol Compound (D) ]
In one embodiment, the polymerizable composition for optical materials contains a polyol compound (D) having 2 or more hydroxyl groups, as needed. The polyol compound (D) is a polyol having 2 or more hydroxyl groups, in other words, a diol (bifunctional) or more.
Examples of the polyol compound as the dihydric or higher polyhydric alcohol include 1, 2-ethanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, diethylene glycol, dipropylene glycol, higher polyalkylene glycol, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, tricyclohexyldimethanol, tricyclodecanedimethanol, tripropylene glycol, polypropylene glycol (diol type), polycaprolactone triol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hydroxypropylcyclohexanol, tricyclo [5, 2, 1, 0, 2, 6] decane-dimethanol, Linear, branched or cyclic aliphatic polyols such as bicyclo [4, 3, 0] -nonanediol, dicyclohexyl glycol, tricyclo [5, 3, 1, 1] dodecanediol, bicyclo [4, 3, 0] nonanedimethanol, tricyclo [5, 3, 1, 1] dodecane-diethanol, hydroxypropyl tricyclo [5, 3, 1, 1] dodecanol, spiro [3, 4] octanediol, butylcyclohexanediol, 1,1 '-dicyclohexylidene diol (1, 1' -biscyclohexylidenediol), cyclohexanetriol, maltitol, lactitol and the like;
cyclohexane diethanol dihydroxybenzene, benzenetriol, hydroxybenzyl alcohol, dihydroxytoluene, 4 '-oxo-bisphenol, 4' -dihydroxybenzophenone, 4 '-thiobisphenol, phenolphthalein, bis (4-hydroxyphenyl) methane, 4' - (1, 2-ethenediyl) bisphenol (4, 4 '- (1, 2-ethenediyl) bisphenol), 4' -sulfonylbisphenol, 4 '-isopropylidenebis (2, 6-dibromophenol), 4' -isopropylidenebis (2, 6-dichlorophenol), 4 '-isopropylidenebis (2, 3, 5, 6-tetrachlorophenol), 4' -isopropylidenebis-bicyclohexanol, 4 '-oxybicyclohexanol, 4' -thiobicyclohexanol, Aromatic polyhydric alcohols such as bis (4-hydroxycyclohexanol) methane, but are not limited thereto.
Among them, from the viewpoint of low haze and excellent heat resistance of the obtained resin, it is preferable to use a diol compound (D1) having 2 hydroxyl groups as the polyol compound (D).
Preferably, at least 1 kind selected from the group consisting of a linear aliphatic diol compound, a branched aliphatic diol compound, a cyclic aliphatic diol compound, and an aromatic diol compound is used as the diol compound (d 1).
Among them, from the viewpoint of the workability of the polymerizable composition and the heat resistance of the obtained molded article, it is preferable to use cyclohexane dimethanol, tricyclodecane dimethanol, and polypropylene glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol as the glycol compound (d 1).
(other Components)
The polymerizable composition for optical materials of the present embodiment may further contain additives such as a polymerization catalyst, an internal mold release agent, a resin modifier, a light stabilizer, a bluing agent, an ultraviolet absorber, an antioxidant, a coloring inhibitor, a dye, and a photochromic dye, depending on the characteristics desired in the application.
That is, in order to adjust various physical properties such as optical properties, impact resistance, and specific gravity of the obtained molded article and to adjust the workability of each component of the polymerizable composition, a modifier may be added to the polymerizable composition of the present embodiment within a range not impairing the effects of the present invention.
(polymerization catalyst)
Examples of the catalyst include lewis acids, tertiary amines, organic acids, and amine organic acid salts, and lewis acids, amines, and amine organic acid salts are preferable, and dimethyltin chloride, dibutyltin dichloride, and dibutyltin laurate are more preferable.
(internal mold Release agent)
The polymeric composition of the present embodiment may contain an internal mold release agent for the purpose of improving releasability from a mold after molding.
As the internal mold release agent, acidic phosphate ester can be used. The acidic phosphate ester includes a phosphoric monoester and a phosphoric diester, and each of them may be used alone or in combination of 2 or more.
For example, ZelecUN manufactured by STEPAN, an internal mold release agent for MR manufactured by Mitsui chemical, JP series manufactured by North City chemical industry, PHOSPHANOL series manufactured by Toho chemical industry, AP and DP series manufactured by Daba chemical industry, and the like can be used.
(resin modifier)
In addition, a resin modifier may be added to the polymerizable composition of the present embodiment in order to adjust various physical properties such as optical properties, impact resistance, and specific gravity of the obtained resin and to adjust the viscosity and pot life of the composition, within a range that does not impair the effects of the present invention.
Examples of the resin modifier include episulfide compounds, alcohol compounds other than the above-mentioned polyol compounds, amine compounds other than the above-mentioned amine compounds, epoxy compounds, organic acids and anhydrides thereof, olefin compounds including (meth) acrylate compounds, and the like.
(light stabilizer)
As the light stabilizer, a hindered amine compound can be used. As the hindered amine-based compound, commercially available products include Lowilite76 and Lowilite92 available from Chemtura, Tinuvin144 and Tinuvin292 available from BASF, ADEKA STAB LA-52 and LA-72 available from ADEKA, and JF-95 available from North City chemical industries, respectively.
(bluing agent)
Examples of the bluing agent include those having an absorption band in the orange to yellow wavelength region in the visible light region and having a function of adjusting the hue of an optical material made of a resin. More specifically, bluing agents include substances that appear blue to violet.
(ultraviolet absorber)
Examples of the ultraviolet absorber include benzophenone compounds, triazine compounds, and benzotriazole compounds.
Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2,2 ' -dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, and 2-hydroxy-4-acryloyloxy-2 ', 4 ' -dichlorobenzophenone,
2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ]4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3- (2' -ethyl) hexyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-4-butyloxyphenyl) -6- Triazine-based ultraviolet absorbers such as (2, 4-bis-butyloxyphenyl) -1,3, 5-triazine and 2- (2-hydroxy-4- [ 1-octyloxycarbonylethoxy ] phenyl) -4, 6-bis (4-phenylphenyl) -1,3, 5-triazine,
2- (2H-benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl) -4-tert-octylphenol, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-amylphenol, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, 2- (5-chloro-2H-benzotriazol-2-yl) -2, 4-tert-butylphenol, benzotriazole-based ultraviolet absorbers such as 2, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 1,3, 3-tetramethylbutyl) phenol ], and the like, and preferable examples thereof include benzotriazole-based ultraviolet absorbers of 2- (2H-benzotriazol-2-yl) -4-tert-octylphenol and 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol. These ultraviolet absorbers may be used alone or in combination of 2 or more.
< method for producing polymerizable composition for optical Material >
The polymerizable composition for an optical material of the present embodiment includes an amine compound (a), an iso (thio) cyanate compound (B), and a polythiol compound (C).
In the polymerizable composition for optical materials of the present embodiment, the ratio (a/B) of the number of moles a of amino groups of the amine compound (a) to the number of moles B of isocyanate groups of the isocyanate (thio) cyanate compound (B) is 0.01 to 0.20, preferably 0.01 to 0.18.
By combining the amine compound (a), the iso (thio) cyanate compound (B) and the polythiol compound (C) and satisfying the above molar ratio, a thiourea resin molded product having a high refractive index, which is low in specific gravity, excellent in heat resistance, solvent resistance, impact resistance and light resistance and in which occurrence of optical distortion (striae) is suppressed due to a long pot life of the polymerizable composition, that is, a thiourea resin molded product having an excellent balance of these properties can be obtained more suitably. The polymerizable composition for optical materials of the present embodiment can exhibit the above-described effects of the present invention, and can provide a resin suitable for spectacle lenses.
In addition, from the viewpoint of the effect of the present invention, the ratio ((a + C)/B) of the total number of moles (a + C) of the amino groups in the amine compound (a) and the number of moles (C) of the mercapto groups in the polythiol compound (C) to the number of moles (B) of the isocyanate group in the isocyanate (thio) cyanate compound (B) is 0.70 to 1.30, preferably 0.70 to 1.20, and more preferably 0.90 to 1.10.
When the polyol compound (D) is used, it is preferably used so that the number of moles D of hydroxyl groups in the polyol compound (D) is 0.01 to 0.7, preferably 0.02 to 0.6, relative to the number of moles C of mercapto groups in the polythiol compound (C). When the polyol compound (D) is used, a resin having a high refractive index, and excellent transparency and heat resistance can be obtained without causing a decrease in impact resistance by adjusting the content to fall within the above range.
When the polyol compound (D) is used, the ratio ((a + C + D)/B) of the total number of moles a of amino groups in the amine compound (a), the total number of moles C of mercapto groups in the polythiol compound (C), and the total number of moles D of hydroxyl groups in the polyol compound (D) to the number of moles B of isocyanate groups in the isocyanate (thio) cyanate compound (B) is 0.7 to 1.30, preferably 0.70 to 1.20, and more preferably 0.90 to 1.10.
The number of moles a of amino groups in the amine compound (a), the number of moles B of iso (thio) cyanate groups in the iso (thio) cyanate compound (B), the number of moles C of mercapto groups in the polythiol compound (C), and the number of moles D of hydroxyl groups in the polyol compound (D) can be theoretically determined from the number of functional groups and molecular weight or weight average molecular weight of the compound used, and the amounts of these compounds used. Alternatively, the number of moles can be determined by a method known in the art such as titration.
The polymerizable composition for optical materials of the present embodiment can be produced by the following method: a method of mixing the amine compound (a), the iso (thio) cyanate compound (B), the polythiol compound (C), and other components together; or a method in which the amine compound (a) is reacted with the iso (thio) cyanate compound (B) to obtain a prepolymer, and then the polythiol compound (C) is added to the prepolymer and mixed.
In one embodiment, the polymerizable composition for optical materials can be prepared by the following method: a method of mixing together the amine compound (a), the iso (thio) cyanate compound (B), the polythiol compound (C), the polyol compound (D), and other components used as needed; or a method in which the amine compound (a) is reacted with the iso (thio) cyanate compound (B) to obtain a prepolymer, the polythiol compound (C) is added to the prepolymer, and the polyol compound (D) is added and mixed; a method in which the amine compound (a) is reacted with the iso (thio) cyanate compound (B) to obtain a prepolymer, the polyol compound (D) is added to the prepolymer, and the polythiol compound (C) is then added; or a method in which the amine compound (a) is reacted with the iso (thio) cyanate compound (B) to obtain a prepolymer, and then a mixture of the polythiol compound (C) and the polyol compound (D) is added to the prepolymer.
When the polymerizable composition for optical materials is prepared by mixing all the components, the temperature at which the polymerizable composition is mixed by mixing the amine compound (a), the monomer such as the iso (thio) cyanate compound (B) or the polythiol compound (C), the catalyst, the internal mold release agent, and other additives is usually 25 ℃ or lower. From the viewpoint of pot life of the polymerizable composition, a lower temperature is sometimes preferable. However, when the solubility of the catalyst, the internal mold release agent, and the additive in the monomer is poor, the catalyst, the internal mold release agent, and the additive may be dissolved in the monomer or the resin modifier by heating in advance.
When the polyol compound (D) is used, the polymerizable composition for optical materials can be prepared under the same conditions as described above.
The method for producing a polymerizable composition for optical materials by the prepolymer method comprises a step (i) of reacting an amine compound (A) with a bifunctional or higher iso (thio) cyanate compound (B) to obtain a prepolymer, and a step (ii) of adding and mixing a polythiol compound (C) to the prepolymer. Hereinafter, each step will be explained.
[ Process (i) ]
In the step (i), a predetermined amount of the amine compound (a) is charged into the iso (thio) cyanate compound (B) together or in portions, and these are reacted. The ratio (a/B) of the number of moles a of amino groups in the amine compound (A) to the number of moles B of isocyanate groups in the isocyanate compound (B) is 0.01 to 0.20, preferably 0.01 to 0.18.
When the amine compound (a), the iso (thio) cyanate compound (B) and the polythiol compound (C) are mixed together, the reaction heat increases and the pot life becomes short, so that the workability until the casting molding is deteriorated and the resin molded article obtained may have a wavy line. Further, since polymerization is performed before the components are uniformly dissolved, a resin molded product with impaired transparency may be obtained. As in the present embodiment, by obtaining a prepolymer by reacting the amine compound (a) with the iso (thio) cyanate compound (B), and then adding and mixing the polythiol compound (C) to the prepolymer, a resin molded product having excellent transparency and suppressed striae can be suitably obtained.
The reaction of the amine compound (a) with the iso (thio) cyanate compound (B) may be carried out in the presence of an additive. The reaction temperature is not limited to a general one because it varies depending on the kind of the compound and the additive to be used, the amount to be used, and the properties of the prepolymer to be produced, and may be appropriately selected in consideration of the handling property, safety, convenience, and the like.
[ Process (ii) ]
In the step (ii), the polythiol compound (C) is further added to the prepolymer obtained in the step (i) and mixed to obtain a polymerizable composition. The mixing temperature is not limited to a general one because it varies depending on the compound used, and may be appropriately selected in consideration of handling, safety, convenience, and the like, and is preferably 25 ℃ or less. Heating may be performed depending on the solubility of the compound used. The heating temperature may be determined in consideration of stability and safety of the compound.
When a prepolymer is obtained from the iso (thio) cyanate compound (B) and the polythiol compound (C) in the step (i), and the amine compound (a) is added to and mixed with the prepolymer obtained in the step (i) in the subsequent step (ii) to obtain a polymerizable composition, the prepolymer obtained in the step (i) has an isocyanate group residue, and therefore the reaction heat with the amine compound (a) increases, and the pot life becomes short. Therefore, the workability until the casting molding is remarkably lowered, and a rib may be generated in the obtained resin molded product.
In contrast, according to the above-mentioned method for producing a polymerizable composition for an optical material by the prepolymer method, since the prepolymer is obtained by reacting the amine compound (a) and the iso (thio) cyanate compound (B) in the step (i) at the molar ratio a/B within the above range, the amino group of the amine compound (a) hardly remains, and therefore, the above-mentioned problem does not occur.
The molded body can be obtained by curing the polymerizable composition for an optical material of the present embodiment.
When the polyol compound (D) is used, it is preferable to add and mix the prepolymer obtained in the step (i) during the step (ii) as described above. The polyol compound (D) may be added before, after, or simultaneously with the addition of the polythiol compound (C), or a mixture of the polythiol compound (C) and the polyol compound (D) may be added to the prepolymer.
< method for producing optical Material >
In the present embodiment, the optical material formed of the thiourea resin molded body is not particularly limited, and can be obtained by casting polymerization including the following steps as a preferable production method.
Step a 1: the polymerizable composition for optical materials of the present embodiment is injected into a mold.
Step b 1: the polymerizable composition for an optical material is heated to polymerize and cure the composition, thereby obtaining a cured product (a thiourea resin molded product).
[ Process a1]
First, a polymerizable composition is injected into a molding die (mold) held by a gasket, a tape, or the like. In this case, depending on the physical properties required for the plastic lens to be obtained, it is often preferable to perform a defoaming treatment under reduced pressure, a filtration treatment such as pressurization or depressurization, and the like, as necessary.
[ Process b1]
The polymerization conditions are not limited since the conditions vary greatly depending on the composition of the polymerizable composition, the type and amount of the catalyst used, the shape of the mold, and the like, and are generally carried out at a temperature of-50 to 150 ℃ for 1 to 50 hours. In some cases, it is preferable to cure the resin by maintaining or gradually raising the temperature within a temperature range of 10 to 150 ℃ for 1 to 25 hours.
The optical material formed of the thiourea resin of the present embodiment may be subjected to a treatment such as annealing, if necessary. The treatment temperature is usually 50 to 150 ℃, preferably 90 to 140 ℃, and more preferably 100 to 130 ℃.
In the present embodiment, when an optical material made of a thiourea resin is molded, various additives such as a chain extender, a crosslinking agent, an oil-soluble dye, a filler, and an adhesion improver can be added in addition to the above-mentioned "other components" in accordance with the purpose in the same manner as in the known molding method.
The polymerizable composition of the present embodiment can be obtained as an optical material having various shapes by changing a mold for casting polymerization. The optical material of the present embodiment can be formed into various shapes by forming the optical material into a desired shape and providing a coating layer, other members, and the like formed as necessary.
< Plastic spectacle lens >
The optical material obtained by curing the polymerizable composition for an optical material of the present embodiment can be used as a lens base material for a spectacle lens. If necessary, a coating layer may be applied to one or both surfaces of the lens substrate. Examples of the coating layer include a hard coat layer, an antireflection layer, an antifogging coating layer, an antifouling layer, a water-repellent layer, an undercoat layer, and a photochromic layer. These coating layers may be used alone or a plurality of coating layers may be formed in a multilayer manner. When applying the coating layers on both sides, the same coating layer may be applied on each side, or different coating layers may be applied.
When the optical material of the present embodiment is applied to a spectacle lens, a hard coat layer and/or an antireflection coating layer may be formed on at least one surface of the optical material (lens base material) obtained by curing the polymerizable composition of the present embodiment. In addition, other layers described above may also be provided. The spectacle lens obtained as described above is excellent in impact resistance even when provided with such a coating layer because it uses a lens formed from the specific polymerizable composition of the present invention.
The hard coat layer is a coating layer provided on at least one surface of an optical material (lens base material) obtained by curing the polymerizable composition of the present embodiment, and is intended to impart functions such as scratch resistance, abrasion resistance, moisture resistance, hot water resistance, heat resistance, and light resistance to the surface of the obtained spectacle lens. The hard coat layer is obtained from a composition comprising: 1 or more metal oxides selected from the group consisting of silicon, titanium, zirconium, tin, aluminum, tungsten, and antimony; and a silane compound having at least 1 or more functional groups selected from the group consisting of alkyl groups, allyl groups, alkoxy groups, methacryloyloxy groups, acryloyloxy groups, epoxy groups, amino groups, isocyanate groups, and mercapto groups, and a hydrolysate thereof.
In the hard coating composition, a curing agent may be included for the purpose of promoting curing. Specific examples of the curing agent include inorganic acids, organic acids, amines, metal complexes, organic acid metal salts, metal chlorides, and the like. A solvent may be used in preparing the hard coating composition. Specific examples of the solvent include water, alcohols, ethers, ketones, and esters.
The hard coat layer can be formed by applying the hard coat composition to the surface of the lens substrate by a known coating method such as spin coating, dip coating, or the like, and then curing it. Examples of the curing method include thermal curing and curing methods by irradiation with energy rays such as ultraviolet rays and visible rays. In the case of heat curing, the curing is preferably carried out at 80 to 120 ℃ for 1 to 4 hours. In order to suppress the occurrence of interference fringes, the difference between the refractive index of the hard coat layer and the refractive index of the molded body is preferably within ± 0.1.
Before the hard coat layer is provided, the surface of the lens base material is preferably ultrasonically cleaned with an aqueous alkali solution so as to satisfy the following conditions (a) to (d).
(a) The alkaline water solution is 5-40% sodium hydroxide or potassium hydroxide water solution,
(b) the treatment temperature of the alkaline water solution is 30-60 ℃,
(c) the treatment time is 3 to 5 minutes,
(d) the frequency of the ultrasonic wave is 20-30 kHz.
After washing with an aqueous alkali solution, the surface of the lens base material may be washed with distilled water, alcohol such as isopropyl alcohol, or the like, and dried at 50 to 80 ℃ for 5 to 20 minutes.
The lens base material composed of the molded article obtained from the polymerizable composition of the present embodiment is excellent in alkali resistance, and can suppress the generation of white turbidity and the like even after washing with an aqueous alkali solution.
The antireflection layer is a coating layer provided on at least one surface of the molded body (lens base material) for the purpose of reducing the reflectance due to the difference in refractive index between air and the molded body, greatly reducing the reflection of light on the surface of the obtained plastic spectacle lens, and improving the transmittance. The antireflection layer in this embodiment is formed of a low refractive index film layer containing silicon oxide and a high refractive index film layer containing 1 or more metal oxides selected from titanium oxide, zirconium oxide, aluminum oxide, zinc oxide, cerium oxide, antimony oxide, tin oxide, and tantalum oxide, and each layer may have a single-layer or multi-layer structure.
When the antireflection layer has a multilayer structure, it is preferable that 5 to 7 layers are stacked. The film thickness is preferably 100 to 300nm, and more preferably 150 to 250 nm. Examples of the method for forming the multi-layer antireflection layer include a vacuum deposition method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, and the like.
An antifogging coating layer, an anti-fouling layer, and a hydrophobic layer may be formed on the antireflection layer as required. As a method for forming the antifogging coating layer, the anti-staining layer, the water-repellent layer, the treatment method thereof, the treatment material, and the like are not particularly limited as long as they do not adversely affect the anti-reflection function, and known antifogging coating treatment method, anti-staining treatment method, water-repellent treatment method, material can be used. For example, as the anti-fog coating and anti-fouling treatment method, there are a method of coating the surface with a surfactant, a method of adding a hydrophilic film to the surface to make the surface water-absorbing, a method of coating the surface with fine irregularities to improve the water-absorbing property, a method of making the surface water-absorbing by utilizing the photocatalytic activity, and a method of performing a superhydrophobic treatment to prevent adhesion of water droplets. Examples of the water repellent treatment method include a method of forming a water repellent treatment layer by vapor deposition or sputtering of a fluorine-containing silane compound, and a method of forming a water repellent treatment layer by dissolving a fluorine-containing silane compound in a solvent and then coating the solution.
Ultraviolet absorbers for the purpose of protecting lenses and eyes from ultraviolet rays may be incorporated in these coating layers; infrared absorbers for the purpose of protecting the eyes from infrared rays; light stabilizers, antioxidants for the purpose of improving the weatherability of lenses; dyes, pigments, and photochromic dyes, photochromic pigments for the purpose of improving the fashion of lenses; an antistatic agent; other known additives for improving the performance of the lens. As for the layer to be coated by coating, various leveling agents for the purpose of improving coatability can be used.
For the purpose of fashion and photochromic property, the optical material using the polymerizable composition of the present embodiment can be dyed using a coloring matter corresponding to the purpose. The dyeing of the lens can be carried out by a known dyeing method, and can be generally carried out by the method shown below.
Generally, the following methods can be utilized: the lens blank finished into a predetermined optical surface is immersed in a dyeing solution in which a pigment to be used is dissolved or uniformly dispersed (dyeing step), and then the lens is heated as necessary to fix the pigment (post-dyeing annealing step). The coloring matter used in the dyeing step is not particularly limited as long as it is a known coloring matter, and generally, an oil-soluble dye or a disperse dye can be used. The solvent used in the dyeing step is not particularly limited as long as the pigment used can be dissolved or uniformly dispersed. In the dyeing step, a surfactant for dispersing the dye in the dyeing liquid and a carrier for accelerating dyeing may be added as necessary.
In the dyeing step, a dye and a surfactant added as needed are dispersed in water or a mixture of water and an organic solvent to prepare a dyeing bath, and the optical lens is immersed in the dyeing bath and dyed at a predetermined temperature for a predetermined time. The dyeing temperature and time vary depending on the desired coloring concentration, and generally, the temperature may be set to 120 ℃ or lower for several minutes to several tens of hours, and the dye concentration in the dyeing bath may be set to 0.01 to 10% by weight. In addition, when dyeing is difficult, it can be carried out under pressure.
The post-dyeing annealing step, which is performed as necessary, is a step of heat-treating the dyed lens blank. In the heating treatment, water remaining on the surface of the lens blank dyed in the dyeing step is removed with a solvent or the like, or the solvent is dried in the air, and then the lens blank is left in a furnace such as an infrared heating furnace or a resistance heating furnace in an atmospheric atmosphere for a predetermined time. The post-dyeing annealing step can remove moisture that has penetrated into the lens blank during dyeing, as well as prevent discoloration of the dyed lens blank (discoloration prevention treatment). In the present embodiment, when the alcohol compound is not contained, unevenness after dyeing is small.
< Plastic polarizing lens >
The optical material obtained by curing the polymerizable composition for an optical material of the present embodiment can be used as a lens base material for a plastic polarizing lens. In one embodiment, a plastic polarizing lens includes: a polarizing film; and a base material layer (lens base material) formed on at least one surface of the polarizing film and formed of a molded body obtained by curing the polymerizable composition for optical materials of the present embodiment.
The polarizing film in the present embodiment may be composed of a thermoplastic resin. Examples of the thermoplastic resin include polyester resins, polycarbonate resins, polyolefin resins, polyimide resins, polyvinyl alcohol resins, and polyvinyl chloride resins. From the viewpoint of water resistance, heat resistance and molding processability, polyester resins and polycarbonate resins are preferred, and polyester resins are more preferred.
The polyester resin includes polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and the like, and polyethylene terephthalate is preferable from the viewpoint of water resistance, heat resistance, and moldability.
Specific examples of the polarizing film include a polyester polarizing film containing a dichroic dye, a polyvinyl alcohol polarizing film containing iodine, and a polyvinyl alcohol polarizing film containing a dichroic dye.
The polarizing film may be used after being subjected to heat treatment for drying and stabilization.
In addition, the polarizing film may be used after being subjected to 1 or 2 or more kinds of pretreatment selected from undercoating treatment, chemical treatment (chemical treatment such as gas or alkali treatment), corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, roughening treatment, flame treatment, and the like, in order to improve the adhesion to the acrylic resin. Among such pretreatment, 1 or 2 or more selected from among undercoating treatment, chemical treatment, corona discharge treatment and plasma treatment are particularly preferable.
In the plastic polarizing lens of the present embodiment, a substrate layer obtained by curing the polymerizable composition for optical materials of the present embodiment may be laminated on one of the object surface side surface or the eye surface side surface of such a polarizing film, or on both the object surface side surface and the eye surface side surface.
The base layer in the present embodiment may contain a layer formed of a plastic material such as an acrylic resin, an allyl carbonate resin, a polycarbonate resin, a polyurethane resin, a polythiourethane resin, or a polythioether resin, in addition to a layer formed of a cured product of the polymerizable composition for an optical material in the present embodiment.
The plastic polarizing lens of the present embodiment is not particularly limited, and can be produced by a method of laminating a lens base material produced in advance on both sides of a polarizing film, a method of cast-polymerizing a polymerizable composition on both sides of a polarizing film, or the like. In this embodiment, an example of formation by a cast polymerization method will be described.
In the present embodiment, the plastic polarizing lens can be obtained by a manufacturing method including the following steps, for example.
Step a 2: in a casting mold for lens casting molding, a polarizing film is fixed in a state where at least one surface of the polarizing film is separated from a mold.
Step b 2: the polymerizable composition of the present embodiment is injected into the gap between the polarizing film and the mold.
Step c 2: the polymerizable composition is heated to polymerize and cure the composition, and a base material layer formed of a cured product of the polymerizable composition of the present embodiment is laminated on at least one surface of the polarizing film.
Hereinafter, each step will be described in order.
[ Process a2]
In the space of the mold for lens casting molding, a polarizing film made of thermoplastic polyester or the like is provided in parallel with the inner surface of the mold facing at least one of the film surfaces. A gap portion is formed between the polarizing film and the mold. The polarizing film may be shaped in advance.
[ Process b2]
Next, the polymerizable composition for optical materials of the present embodiment is injected into the space between the mold and the polarizing film by a predetermined injection means in the space of the mold for lens cast molding.
[ Process c2]
Next, the polarizing film-fixed lens casting mold into which the polymerizable composition for optical materials is injected is heated and cured in a heatable apparatus such as an oven or water for several hours to several tens of hours at a predetermined temperature program.
The temperature for the polymerization and curing is not limited since the conditions vary depending on the composition of the polymerizable composition, the kind of the catalyst, the shape of the mold, and the like, and may be carried out at a temperature of 0 to 140 ℃ for 1 to 48 hours.
After the completion of the curing molding, the plastic polarizing lens of the present embodiment can be obtained by taking out the lens casting mold, and a layer formed by a cured product of the polymerizable composition of the present embodiment is laminated on at least one surface of the polarizing film.
In the plastic polarized lens of the present embodiment, in order to alleviate the deformation caused by polymerization, it is preferable to heat the lens after the mold release and perform annealing treatment.
The plastic polarizing lens of the present embodiment may be used by applying a coating layer to one or both surfaces, as necessary. Examples of the coating layer include an undercoat layer, a hard coat layer, an antireflection layer, an antifogging layer, an antifouling layer, and a hydrophobic layer similar to those of plastic spectacle lenses.
< use >
Next, the use of the optical material of the present embodiment will be explained.
Examples of the optical material described in the present embodiment include plastic spectacle lenses, goggles, spectacle lenses for vision correction, lenses for image pickup devices, fresnel lenses for liquid crystal projectors, lenticular lenses, contact lenses, and other various plastic lenses, sealing materials for Light Emitting Diodes (LEDs), optical waveguides, optical adhesives for joining optical lenses and optical waveguides, antireflection films for optical lenses and other optical lenses, transparent coatings for liquid crystal display device members (substrates, light guide plates, films, sheets, and the like), and sheets, films, and transparent substrates for bonding to windshields of automobiles and helmets.
The present invention has been described above by way of embodiments, but the present invention is not limited to the above-described embodiments, and various embodiments can be adopted within a range not impairing the effects of the present invention.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
First, the evaluation method in the example of the present invention is shown below.
< evaluation method >
Transparency: the obtained resin was irradiated with a spotlight (projector) in a dark place, and the presence or absence of fogging (including elution from the tape) and an opaque substance was visually checked. The case where fogging (including elution from the tape) was not observed and the case where the opaque substance was observed was marked as "o" (transparency), and the case where fogging (including elution from the tape) was observed and the case where the opaque substance was observed was marked as "x" (non-transparency).
HAZE (HAZE): the haze value of the resin was measured on a 2.5mm thick plate using a haze meter (model: NDH 2000) manufactured by Nippon Denshoku industries Co., Ltd. When the haze value is less than 0.70, the lens can be used without any problem.
Deformation (beads): when the obtained lens was projected by a high-pressure UV lamp, the case where no deformation was observed in the lens was "very excellent" (no striae), the case where no deformation was observed in the lens by visual observation was "o", and the case where deformation was observed in the lens by visual observation was "x" (striae).
Refractive index (ne), abbe number (ve): the measurement was carried out at 20 ℃ using a Pollrich refractometer.
Heat resistance: the glass transition temperature Tg was measured by the TMA penetration method (load: 50g, tip diameter: 0.5mm, heating rate: 10 ℃/min).
Specific weight: the measurement was carried out by the Archimedes method.
Impact resistance: the impact resistance was evaluated by the weight of the steel ball at the time of fracture, after dropping a light steel ball and a heavy steel ball onto a lens having a center thickness of 1mm in order from a height of 127cm, according to the regulations of the U.S. FDA, until the lens was fractured. The steel balls are implemented in the order of 8g → 16g → 28g → 33g → 45g → 67g → 95g → 112g → 174g → 225g → 530 g. In the table, the expression "> 530 g" indicates that the steel ball of 530g was not broken even when dropped.
Light resistance: QUV test was carried out using a 2mm thick plate using an accelerated weathering tester made by Q-Lab (light source: UVA-340, strength: 0.50W/m)2The test conditions are as follows: 50 ℃ x 200 hours), and the change in hue before and after irradiation was measured.
Solvent resistance: the nonwoven fabric impregnated with acetone was pressed against the surface of the obtained lens for 10 seconds, and the case where no swelling mark was observed on the lens surface was marked as "o" (solvent-resistant), and the case where no swelling mark was observed was marked as "x" (solvent-free).
[ example 1]
50.31 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 10.91 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 18.26 parts by weight of bis (2-mercaptoethyl) sulfide and 20.52 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.58, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 92 ℃, a specific gravity of 1.256, and a light resistance Δ YI of 2.0. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 2]
50.77 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 10.99 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 25.81 parts by weight of bis (2-mercaptoethyl) sulfide and 12.43 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.57, no striae, a refractive index (ne) of 1.596, an Abbe number (ve) of 40, a Tg of 88 ℃, a specific gravity of 1.251, and a light resistance Δ YI of 1.5. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 3]
51.46 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 9.62 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 26.27 parts by weight of bis (2-mercaptoethyl) sulfide and 12.65 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.56, no striae, a refractive index (ne) of 1.599, an Abbe number (ve) of 40, a Tg of 89 ℃, a specific gravity of 1.262 and a light resistance Δ YI of 1.6. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 4]
48.70 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 13.19 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 29.74 parts by weight of bis (2-mercaptoethyl) sulfide and 8.37 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.59, no striae, a refractive index (ne) of 1.596, an Abbe number (ve) of 40, a Tg of 84 ℃, a specific gravity of 1.261 and a light resistance Δ YI of 1.6. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 5]
51.67 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 9.63 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, made by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 30.21 parts by weight of bis (2-mercaptoethyl) sulfide and 8.49 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.57, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 88 ℃, a specific gravity of 1.264 and a light resistance Δ YI of 1.2. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 6]
To 48.94 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged 13.71 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 dropwise, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 17.59 parts by weight of bis (2-mercaptoethyl) sulfide and 19.76 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.58, no striae, a refractive index (ne) of 1.592, an Abbe number (ve) of 41, a Tg of 91 ℃, a specific gravity of 1.254, and a light resistance Δ YI of 1.7. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 7]
To 45.25 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was added dropwise 21.97 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 25.59 parts by weight of bis (2-mercaptoethyl) sulfide and 7.19 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.59, no striae, a refractive index (ne) of 1.597, an Abbe number (ve) of 42, a Tg of 76 ℃, a specific gravity of 1.227, and a light resistance Δ YI of 2.1. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 8]
47.01 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 10.35 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, made by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 23.46 parts by weight of 2, 5-bis (mercaptomethyl) -1, 4-dithiane and 19.18 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.57, no striae, a refractive index (ne) of 1.604, an Abbe number (ve) of 40, a Tg of 110 ℃, a specific gravity of 1.280 and a light resistance Δ YI of 2.1. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 9]
To 46.20 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise 10.22 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 32.28 parts by weight of 2, 5-bis (mercaptomethyl) -1, 4-dithiane and 11.30 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.56, no striae, a refractive index (ne) of 1.604, an Abbe number (ve) of 40, a Tg of 113 ℃, a specific gravity of 1.283 and a light resistance Δ YI of 2.1. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 10]
To 45.24 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged 14.22 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 dropwise, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 22.31 parts by weight of 2, 5-bis (mercaptomethyl) -1, 4-dithiane and 18.23 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.58, no striae, a refractive index (ne) of 1.596, an Abbe number (ve) of 40, a Tg of 106 ℃, a specific gravity of 1.268 and a light resistance Δ YI of 2.1. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 11]
To 44.50 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged 14.02 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 dropwise, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 30.72 parts by weight of 2, 5-bis (mercaptomethyl) -1, 4-dithiane and 10.76 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.58, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 110 ℃, a specific gravity of 1.271 and a light resistance Δ YI of 2.1. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 12]
To 50.44 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise 10.93 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 29.29 parts by weight of bis (2-mercaptoethyl) sulfide and 9.34 parts by weight of a mixture of 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane and 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.54, no striae, a refractive index (ne) of 1.597, an Abbe number (ve) of 40, a Tg of 86 ℃, a specific gravity of 1.256, and a light resistance Δ YI of 1.5. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 13]
To 49.51 parts by weight of 1, 3-bis (isocyanatomethyl) cyclohexane was added 11.35 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, made by Huntsman corporation) having a weight average molecular weight of 2000 dropwise, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and 30.56 parts by weight of bis (2-mercaptoethyl) sulfide and 8.58 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.57, no striae, a refractive index (ne) of 1.591, an Abbe number (ve) of 40, a Tg of 75 ℃, a specific gravity of 1.242 and a light resistance Δ YI of 2.0. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 14]
51.12 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 16.52 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-400 manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 400, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 25.26 parts by weight of bis (2-mercaptoethyl) sulfide and 7.10 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.52, no striae, a refractive index (ne) of 1.606, an Abbe number (ve) of 37, a Tg of 79 ℃, a specific gravity of 1.238, and a light resistance Δ YI of 2.0. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 15]
To a mixed solution of 47.85 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2.40 parts by weight of 1, 3-bis (isocyanotomethyl) cyclohexane was added dropwise 10.93 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 18.28 parts by weight of bis (2-mercaptoethyl) sulfide and 20.54 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.56, no striae, a refractive index (ne) of 1.597, an Abbe number (ve) of 40, a Tg of 91 ℃, a specific gravity of 1.255 and a light resistance Δ YI of 2.0. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 16]
51.72 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 5.78 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 and 2.63 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-400, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 400, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 18.77 parts by weight of bis (2-mercaptoethyl) sulfide and 21.10 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.54, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 94 ℃, a specific gravity of 1.253, and a light resistance Δ YI of 1.6. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 17]
50.00 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.47 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 and 3.39 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-400, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 400, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 18.16 parts by weight of bis (2-mercaptoethyl) sulfide and 20.98 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.53, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 93 ℃, a specific gravity of 1.256, and a light resistance Δ YI of 1.6. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 18]
52.21 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 5.82 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 and 2.65 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-400, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 400, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 26.54 parts by weight of bis (2-mercaptoethyl) sulfide and 12.78 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.52, no striae, a refractive index (ne) of 1.597, an Abbe number (ve) of 40, a Tg of 90 ℃, a specific gravity of 1.255 and a light resistance Δ YI of 1.5. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 19]
50.77 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.56 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 and 3.43 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-400, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 400, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 25.81 parts by weight of bis (2-mercaptoethyl) sulfide and 12.43 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.52, no striae, a refractive index (ne) of 1.597, an Abbe number (ve) of 40, a Tg of 89 ℃, a specific gravity of 1.256, and a light resistance Δ YI of 1.5. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 20]
50.31 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 10.91 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride, 1.50 parts by weight of an ultraviolet absorber (product of Co., Ltd.; trade name: BIOSORB 583) and 0.60 parts by weight of an internal mold release agent (product of Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 18.26 parts by weight of bis (2-mercaptoethyl) sulfide and 20.52 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.57, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 90 ℃, a specific gravity of 1.256, and a light resistance Δ YI of 0.5. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 21]
50.31 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 10.91 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride, 1.00 parts by weight of an ultraviolet absorber (manufactured by BASF, trade name TINUVIN 326) and 0.60 parts by weight of an internal mold release agent (manufactured by mitsui chemical, trade name MR internal mold release agent) were mixed and dissolved to prepare a homogeneous solution, and then 18.26 parts by weight of bis (2-mercaptoethyl) sulfide and 20.52 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.57, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 91 ℃, a specific gravity of 1.256, and a light resistance Δ YI of 0.3. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
Comparative example 1
To 56.58 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was mixed and dissolved 0.15 part by weight of dibutyltin dichloride and 0.60 part by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) to prepare a homogeneous solution, and then 33.89 parts by weight of bis (2-mercaptoethyl) sulfide and 9.53 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.51, no striae, a refractive index (ne) of 1.615, an Abbe number (ve) of 38, a Tg of 94 ℃, a specific gravity of 1.289, and a light resistance Δ YI of 8.0. In the impact resistance test, a 112g steel ball was used and fractured. No swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
Comparative example 2
To 53.58 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 32.10 parts by weight of bis (2-mercaptoethyl) sulfide and 14.32 parts by weight of trimethylolpropane tris (3-mercaptopropionate) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.51, no striae, a refractive index (ne) of 1.599, an Abbe number (ve) of 40, a Tg of 90 ℃, a specific gravity of 1.287, and a light resistance Δ YI of 6.3. In the impact resistance test, a 112g steel ball was used and fractured. No swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
Comparative example 3
48.70 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 16.42 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, made by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 34.88 parts by weight of bis (2-mercaptoethyl) sulfide was further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.58, no striae, a refractive index (ne) of 1.585, an Abbe number (ve) of 41, a Tg of 74 ℃, a specific gravity of 1.242, and a light resistance Δ YI of 2.3. In the impact resistance test, 530g of steel balls were used without breaking. However, swelling due to acetone solvent was observed, and the solvent resistance was poor. The results are shown in Table-1.
Comparative example 4
When a mixture of 57.42 parts by weight of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was added dropwise to 11.48 parts by weight of m-xylylenediamine, intense heat was released and a polymer-like insoluble substance was precipitated. Therefore, the subsequent operation cannot be performed. The results are shown in Table-1.
Comparative example 5
47.37 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 14.12 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and thereafter 38.51 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.59, no striae, a refractive index (ne) of 1.595, an Abbe number (ve) of 40, a Tg of 93 ℃, a specific gravity of 1.260, and a light resistance Δ YI of 2.1. In the impact resistance test, a steel ball of 174g was used and fractured. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-1.
[ example 22]
53.85 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 15.55 parts by weight of bis (2-mercaptoethyl) sulfide, 16.60 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 7.00 parts by weight of 1, 4-cyclohexanedimethanol (manufactured by Tokyo chemical Co., Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.50, no striae, a refractive index (ne) of 1.586, an Abbe number (ve) of 42, a Tg of 96 ℃, a specific gravity of 1.252, and a light resistance Δ YI of 1.2. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 23]
To 52.65 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 dropwise, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 16.10 parts by weight of bis (2-mercaptoethyl) sulfide, 17.25 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 7.00 parts by weight of tricyclodecanedimethanol (manufactured by Tokyo chemical Co., Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.50, no striae, a refractive index (ne) of 1.591, an Abbe number (ve) of 41, a Tg of 97 ℃, a specific gravity of 1.258 and a light resistance Δ YI of 1.2. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 24]
53.48 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 17.65 parts by weight of bis (2-mercaptoethyl) sulfide, 18.87 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 3.00 parts by weight of 1, 4-cyclohexanedimethanol (manufactured by Tokyo chemical Co., Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.57, no striae, a refractive index (ne) of 1.594, an Abbe number (ve) of 41, a Tg of 90 ℃, a specific gravity of 1.253, and a light resistance Δ YI of 1.5. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 25]
53.79 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 14.12 parts by weight of bis (2-mercaptoethyl) sulfide, 15.09 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 10.00 parts by weight of 1, 4-cyclohexanedimethanol (manufactured by Tokyo chemical Co., Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.32, no striae, a refractive index (ne) of 1.581, an Abbe number (ve) of 42, a Tg of 103 ℃, a specific gravity of 1.250, and a light resistance Δ YI of 1.2. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 26]
To 52.98 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by Huntsman Co., Ltd.) having a weight average molecular weight of 2000 dropwise, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 17.89 parts by weight of bis (2-mercaptoethyl) sulfide, 19.13 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 3.00 parts by weight of tricyclodecanedimethanol (manufactured by Tokyo chemical Co., Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.56, no striae, a refractive index (ne) of 1.598, an Abbe number (ve) of 40, a Tg of 91 ℃, a specific gravity of 1.253, and a light resistance Δ YI of 1.3. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 27]
52.15 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 14.91 parts by weight of bis (2-mercaptoethyl) sulfide, 15.94 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 10.00 parts by weight of tricyclodecanedimethanol (manufactured by Tokyo chemical Co., Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.31, no striae, a refractive index (ne) of 1.588, an Abbe number (ve) of 41, a Tg of 105 ℃, a specific gravity of 1.251, and a light resistance Δ YI of 1.2. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 28]
57.93 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 13.57 parts by weight of bis (2-mercaptoethyl) sulfide, 14.50 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 7.00 parts by weight of propylene glycol (manufactured by Wako pure chemical industries, Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.61, and was visually observed to have no distortion in the lens, a refractive index (ne) of 1.576, an Abbe number (ve) of 43, a Tg of 95 ℃, a specific gravity of 1.251, and a light resistance Δ YI of 1.3. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 29]
54.22 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 15.36 parts by weight of bis (2-mercaptoethyl) sulfide, 16.42 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 7.00 parts by weight of dipropylene glycol (manufactured by Wako pure chemical industries, Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.69, no striae, a refractive index (ne) of 1.583, an Abbe number (ve) of 42, a Tg of 90 ℃, a specific gravity of 1.253, and a light resistance Δ YI of 1.5. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 30]
52.73 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 16.08 parts by weight of bis (2-mercaptoethyl) sulfide, 17.19 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 7.00 parts by weight of tripropylene glycol (manufactured by Wako pure chemical industries, Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.69, no striae, a refractive index (ne) of 1.586, an Abbe number (ve) of 41, a Tg of 86 ℃, a specific gravity of 1.255, and a light resistance Δ YI of 1.6. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ example 31]
51.20 parts by weight of a mixture of 2, 5-bis (isocyanotomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanotomethyl) bicyclo [2.2.1] heptane was charged dropwise with 7.00 parts by weight of poly (propylene glycol) bis (2-aminopropyl ether) (Jeffamine D-2000, made by Huntsman corporation) having a weight average molecular weight of 2000, and the reaction was carried out at 20 ℃ for 1 hour. To this solution, 0.15 parts by weight of dibutyltin dichloride and 0.60 parts by weight of an internal mold release agent (manufactured by Mitsui chemical Co., Ltd.; trade name: internal mold release agent for MR) were mixed and dissolved to prepare a homogeneous solution, and then 20.30 parts by weight of bis (2-mercaptoethyl) sulfide, 14.50 parts by weight of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 7.00 parts by weight of polypropylene glycol (glycol type, molecular weight of about 400, manufactured by Wako pure chemical industries, Ltd.) were further mixed and dissolved to prepare a homogeneous solution. Defoaming was performed at 400Pa, and then, the mixture was injected into a molding die. The resulting mixture was put into a polymerization oven, and polymerization was carried out by gradually raising the temperature from 25 ℃ to 120 ℃ over 24 hours. After the polymerization, the molded article was taken out of the oven and released from the mold. The releasability was good, and no mold separation was observed. The molded article obtained was further annealed at 120 ℃ for 1 hour. The obtained molded article had transparency, had a haze value of 0.69, no striae, a refractive index (ne) of 1.589, an Abbe number (ve) of 41, a Tg of 81 ℃, a specific gravity of 1.254, and a light resistance Δ YI of 1.6. In the impact resistance test, 530g of steel balls were used without breaking. Further, no swelling due to acetone solvent was observed, and the solvent resistance was good. The results are shown in Table-2.
[ Table 1]
TABLE-1
Figure BDA0001994707060000521
[ Table 2]
Watch-1 (continue)
Figure BDA0001994707060000531
[ Table 3]
TABLE-2
Figure BDA0001994707060000541
[ Table 4]
Watch-2 (continue)
Figure BDA0001994707060000542
The symbols in the table indicate the following meanings.
*1: the ratio (a/B) of the number of moles a of amino groups in the amine compound (A) to the number of moles B of isocyanate groups in the isocyanate (thio) cyanate compound (B)
*2: the ratio of the number of moles of dithiol compound (C1) to the number of moles of polythiol compound (C2) contained in polythiol compound (C)
*3: the ratio of the number of moles D of hydroxyl groups in the polyol compound (D) to the number of moles C of mercapto groups in the polythiol compound (C)
The above-mentioned values are theoretical values calculated based on the amount of each compound used, and assuming that the purity of the compound is 100%.
(amine Compound (A))
A1: poly (propylene glycol) bis (2-aminopropyl ether) having a weight average molecular weight of 2000 (Jeffamine D-2000, manufactured by HUNTSMAN Co., Ltd.)
A2: poly (propylene glycol) bis (2-aminopropyl ether) having a weight average molecular weight of 400 (Jeffamine D-400 manufactured by Huntsman Co., Ltd.)
A3: m-xylylenediamine
(iso (thio) cyanate Compound (B))
I1: mixtures of 2, 5-bis (isocyanatomethyl) bicyclo [2.2.1] heptane and 2, 6-bis (isocyanatomethyl) bicyclo [2.2.1] heptane
12: 1, 3-bis (isocyanatomethyl) cyclohexane
(polythiol Compound (C))
T1: bis (2-mercaptoethyl) sulfide
T2: 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane
T3: 2, 5-bis (mercaptomethyl) -1, 4-dithiane
T4: mixtures of 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane and 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane
T5: trimethylolpropane tris (3-mercaptopropionate)
(polyol Compound (D))
P1: 1, 4-cyclohexanedimethanol (manufactured by Tokyo Kabushiki Kaisha)
P2: dicyclodecane dimethanol (manufactured by Tokyo Kabushiki Kaisha)
P3: propylene glycol (Heguang pure chemical industry Co., Ltd.)
P4: dipropylene glycol (Heguang pure chemical industry Co., Ltd.)
P5: tripropylene glycol (Heguang pure chemical industry Co., Ltd.)
P6: polypropylene glycol (diol type, molecular weight about 400, manufactured by Wako pure chemical industries, Ltd.)
The molded thiosemicarbazide products of examples 1 to 21 had a lower specific gravity, and were superior in impact resistance and light resistance and in the balance of these characteristics, as compared with comparative examples 1 and 2, which were molded thiosemicarbazides.
Furthermore, the thiourea molded products of examples 1 to 21 were superior in solvent resistance to the thiourea molded product using only dithiol (comparative example 3), and were superior in impact resistance to the thiourea molded product using only trifunctional thiol (comparative example 5).
In addition, in the combination of the aromatic primary amine and the isocyanate compound (comparative example 4), heat was drastically released, and insoluble substances in the form of a polymer were precipitated, and a resin molded body could not be obtained.
The thiourea molded products using the polyol in examples 22 to 31 had the same degree of impact resistance as the thiourea molded products in examples 1 to 21, and were excellent in heat resistance and transparency, had a high refractive index, and were excellent in balance of these properties.
As described above, the thiourea molded product obtained from the polymerizable composition for an optical material of the present invention has a low specific gravity, is excellent in heat resistance, impact resistance and light resistance, is suppressed in the occurrence of optical distortion (striae), is excellent in light resistance, and is excellent in the balance of these characteristics.
The thiourea molded product obtained from the polymerizable composition for optical materials of the present invention can be suitably used for various optical materials requiring high transparency, particularly spectacle lenses.
The present application claims priority based on Japanese application laid-open at 2016, 25/10, 2016, and 208962, the entire disclosure of which is incorporated herein.

Claims (16)

1. A polymerizable composition for optical materials, comprising:
(A) at least 1 amine compound selected from the group consisting of the compound (a1) represented by the general formula (1) and the compound (a2) represented by the general formula (2),
(B) an isocyanate (thio) cyanate compound having 2 or more isocyanate (thio) groups, and
(C) a polythiol compound comprising a dithiol compound (c1) having 2 mercapto groups and a polythiol compound (c2) having 3 or more mercapto groups,
wherein the compound (a1) represented by the general formula (1) has a weight average Molecular Weight (MW) of 200 to 4000,
the weight-average Molecular Weight (MW) of the compound (a2) represented by the general formula (2) is 400 to 5000,
the ratio (a/B) of the number of moles a of amino groups in the amine compound (A) to the number of moles B of isocyanate groups in the isocyanate compound (B) is in the range of 0.01 to 0.20,
the isocyanate group is an isocyanate group or an isothiocyanate group, the isocyanate compound is an isocyanate compound or an isothiocyanate compound,
[ chemical formula 1]
Figure FDA0003011582940000011
In the general formula (1), R3～R5Each represents a hydrogen atom or a methyl group, p represents an integer of 0 to 100, q represents an integer of 0 to 100, R represents an integer of 1 to 100, p + R satisfies an integer of 1 to 100, and a plurality of R's are present4Each other or R5May be the same as or different from each other,
[ chemical formula 2]
Figure FDA0003011582940000012
In the general formula (2), R6、R8、R9Each represents a hydrogen atom or a methyl group, R7Represents a C1-20 straight-chain alkyl group, a C3-20 branched-chain alkyl group or a C3-20 cyclic alkyl group, x + y + z represents an integer of 1-200, n represents an integer of 0-10, and a plurality of R are present6Each other, R8Each other or R9May be the same or different from each other.
2. The polymerizable composition for optical materials according to claim 1, further comprising a polyol compound (D) having 2 or more hydroxyl groups.
3. The polymerizable composition for optical materials according to claim 1 or 2, wherein the ratio (c1/c2) of the molar number c1 of mercapto groups of the polythiol compound (c1) to the molar number c2 of mercapto groups of the polythiol compound (c2) is in the range of 1 to 13.
4. The polymerizable composition for optical materials as claimed in claim 1 or 2, wherein the dithiol compound (c1) is at least 1 selected from the group consisting of 2, 5-dimercaptomethyl-1, 4-dithiane, ethylene glycol bis (3-mercaptopropionate), 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiacyclobutane and bis (2-mercaptoethyl) sulfide,
the polythiol compound (c2) is selected from trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, at least 1 member of the group consisting of 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, and 1,1,3, 3-tetrakis (mercaptomethylthio) propane.
5. The polymerizable composition for optical materials according to claim 1 or 2, wherein the iso (thio) cyanate ester compound (B) is at least 1 selected from the group consisting of 1, 6-hexamethylene diisocyanate, 1, 5-pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4, 4 '-diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, toluene diisocyanate, benzene diisocyanate, and 4, 4' -diphenylmethane diisocyanate.
6. The polymerizable composition for optical materials according to claim 2, wherein the polyol compound (D) comprises a diol compound (D1) having 2 hydroxyl groups.
7. The polymerizable composition for optical materials as claimed in claim 6, wherein the diol compound (d1) contains at least 1 selected from the group consisting of a linear aliphatic diol compound, a branched aliphatic diol compound, a cyclic aliphatic diol compound, and an aromatic diol compound.
8. The polymerizable composition for optical materials as claimed in claim 6 or 7, wherein the diol compound (d1) is at least 1 selected from the group consisting of cyclohexanedimethanol, tricyclodecanedimethanol and polypropylene glycol.
9. A molded article obtained by curing the polymerizable composition for optical materials according to any one of claims 1 to 8.
10. An optical material formed from the molded body according to claim 9.
11. A plastic lens formed from the molded article according to claim 9.
12. A plastic polarized lens, comprising:
a polarizing film; and
a base material layer formed of the molded body of claim 9, the base material layer being formed on at least one side of the polarizing film.
13. A method for producing a polymerizable composition for optical materials, comprising the steps of:
a step (i) in which at least 1 amine compound (a) selected from the group consisting of an amine compound (a1) represented by general formula (1) and an amine compound (a2) represented by general formula (2) is reacted with an isocyanate compound (B) having 2 or more isocyanate (thio) groups to obtain a prepolymer; and
a step (ii) of adding and mixing a polythiol compound (C) comprising a dithiol compound (C1) having 2 mercapto groups and a polythiol compound (C2) having 3 or more mercapto groups to the prepolymer,
wherein the compound (a1) represented by the general formula (1) has a weight average Molecular Weight (MW) of 200 to 4000,
the weight-average Molecular Weight (MW) of the compound (a2) represented by the general formula (2) is 400 to 5000,
the ratio (a/B) of the number of moles a of amino groups in the amine compound (A) to the number of moles B of isocyanate groups in the isocyanate compound (B) is in the range of 0.01 to 0.20,
the isocyanate group is an isocyanate group or an isothiocyanate group, the isocyanate compound is an isocyanate compound or an isothiocyanate compound,
[ chemical formula 3]
Figure FDA0003011582940000041
In the general formula (1), R3～R5Each represents a hydrogen atom or a methyl group, p represents an integer of 0 to 100, q represents an integer of 0 to 100, R represents an integer of 1 to 100, p + R satisfies an integer of 1 to 100, and a plurality of R's are present4Each other or R5May be the same as or different from each other,
[ chemical formula 4]
Figure FDA0003011582940000042
In the general formula (2), R6、R8、R9Each represents a hydrogen atom or a methyl group, R7Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, x + y + z represents an integer of 1 to 100, n represents an integer of 0 to 10, and a plurality of R are present6Each other, R8Each other or R9May be the same or different from each other.
14. The method for producing a polymerizable composition for optical materials according to claim 13, wherein the step (ii) further comprises a step of adding and mixing a polyol compound (D) having 2 or more hydroxyl groups to the prepolymer obtained in the step (i).
15. A method for producing an optical material, comprising the steps of:
a step of injecting the polymerizable composition for optical materials according to any one of claims 1 to 8 into a mold; and
and a step of polymerizing and curing the polymerizable composition for an optical material in the mold.
16. A method for manufacturing a plastic polarized lens, comprising the steps of:
a step of fixing the polarizing film in a mold for lens casting molding in a state where at least one surface of the polarizing film is separated from the mold;
a step of injecting the polymerizable composition for optical materials according to any one of claims 1 to 8 into a space between the polarizing film and the mold; and
and a step of polymerizing and curing the polymerizable composition for optical materials, and laminating a base material layer formed of a cured product of the polymerizable composition for optical materials on at least one surface of the polarizing film.
CN201780056510.2A 2016-10-25 2017-10-24 Polymerizable composition for optical material, optical material obtained from the composition, and method for producing the same Active CN109715693B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016208962 2016-10-25
JP2016-208962 2016-10-25
PCT/JP2017/038276 WO2018079518A1 (en) 2016-10-25 2017-10-24 Polymerizable composition for optical material, optical material obtained from said composition, and method for producing said composition

Publications (2)

Publication Number Publication Date
CN109715693A CN109715693A (en) 2019-05-03
CN109715693B true CN109715693B (en) 2021-07-09

Family

ID=62023556

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780056510.2A Active CN109715693B (en) 2016-10-25 2017-10-24 Polymerizable composition for optical material, optical material obtained from the composition, and method for producing the same

Country Status (6)

Country Link
US (2) US10563003B2 (en)
EP (1) EP3533817B1 (en)
JP (2) JP2018070865A (en)
KR (1) KR102172909B1 (en)
CN (1) CN109715693B (en)
WO (1) WO2018079518A1 (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019117305A1 (en) * 2017-12-15 2019-06-20 Mitsui Chemicals, Inc. Polymerizable composition for optical materials and application of same
JP7012821B2 (en) 2018-03-16 2022-01-28 三井化学株式会社 A method for producing a polymerizable composition for an optical material, a method for producing a polymerizable composition for an optical material, and a method for producing an optical article.
JP7160649B2 (en) * 2018-11-27 2022-10-25 三井化学株式会社 Polymerizable composition for optical material and optical material obtained from said composition
JP2020139096A (en) * 2019-03-01 2020-09-03 三井化学株式会社 Polymerizable composition for optical material, optical material obtained from the composition and its production method
JP2020164636A (en) * 2019-03-29 2020-10-08 三井化学株式会社 Polymerizable composition for optical material, molding, optical material, plastic lens, and laminated plastic lens
US11807755B2 (en) * 2019-03-29 2023-11-07 Mitsui Chemicals, Inc. Polymerizable composition for optical material, molded product, optical material, plastic lens, and laminated plastic lens
KR20210116710A (en) * 2020-01-27 2021-09-27 미쓰이 가가쿠 가부시키가이샤 Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product and manufacturing method of optical material
CN115286758A (en) 2020-01-27 2022-11-04 三井化学株式会社 Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product, and method for producing optical material
CN116157720A (en) * 2020-12-25 2023-05-23 三井化学株式会社 Iso (thio) cyanate compound, polymerizable composition for optical material, molded body, optical material, plastic lens, plastic polarizing lens, method for producing iso (thio) cyanate compound, method for producing polymerizable composition for optical material, method for producing optical material, and method for producing plastic polarizing lens
WO2022138865A1 (en) * 2020-12-25 2022-06-30 三井化学株式会社 Polythiol composition, polymerizable composition, resin, molded article, optical material, and lens
CN113831502B (en) * 2021-10-22 2023-06-23 东莞市米儿塑胶原料有限公司 Preparation method of high-hardness transparent TPU

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0406161A2 (en) * 1989-06-20 1991-01-02 Ciba-Geigy Ag Fluorine and/or silicone containing poly(alkylene-oxide)-block copolymers and contact lenses thereof
JPH08208794A (en) * 1995-02-03 1996-08-13 Mitsui Toatsu Chem Inc Production of sulfur-containing urethane plastic lens
CN101821309A (en) * 2007-10-15 2010-09-01 三井化学株式会社 Polyurethane resin
EP2227500A2 (en) * 2008-01-02 2010-09-15 Polyplexx, LLC Impact-resistant polyurethanes
CN102918073A (en) * 2010-03-31 2013-02-06 陶氏环球技术有限责任公司 Polyurethane compositions having improved impact resistance and optical properties
US8372939B1 (en) * 2009-08-17 2013-02-12 Polyplexx, Llc Transparent polyurethanes
CN104011103A (en) * 2011-11-18 2014-08-27 三井化学株式会社 Polymerizable composition, optical article obtained therefrom and method for the production of said optical article
WO2016006606A1 (en) * 2014-07-08 2016-01-14 三井化学株式会社 Polymerizable composition for optical material and use thereof
WO2016006605A1 (en) * 2014-07-08 2016-01-14 三井化学株式会社 Polymerizable composition for optical material, and application for same
CN105899563A (en) * 2013-12-10 2016-08-24 Ppg工业俄亥俄公司 Polyurethane urea-containing compositions and optical articles and methods for preparing them

Family Cites Families (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60199016A (en) 1984-03-23 1985-10-08 Mitsui Toatsu Chem Inc Thiocarbomic acid s-alkyl ester resin for lens
US6127505A (en) 1995-02-02 2000-10-03 Simula Inc. Impact resistant polyurethane and method of manufacture thereof
US5962617A (en) 1995-02-02 1999-10-05 Simula Inc. Impact resistant polyurethane and method of manufacture thereof
US20030158369A1 (en) 1995-02-02 2003-08-21 Slagel Edwin C. Impact resistant polyurethane and method of manufacture thereof
IL116963A (en) 1995-02-02 2000-02-17 Simula Inc Impact resistant polyurethane and methods for the manufacture thereof
JPH10186101A (en) * 1996-12-27 1998-07-14 Asahi Opt:Kk Optical high-refractive index plastic lens
CA2391856A1 (en) 1999-11-18 2001-05-25 Ppg Industries Ohio, Inc. Method of preparing an optical polymerizate
US7098290B1 (en) 1999-11-18 2006-08-29 Ppg Industries Ohio, Inc. Method of preparing an optical polymerizate
US7087698B1 (en) 1999-11-18 2006-08-08 Ppg Industries Ohio, Inc. Method of preparing an optical polymerizate
US20070142606A1 (en) 2005-12-16 2007-06-21 Bojkova Nina V Polyurethane (ureas) and sulfur-containing polyurethane (ureas) methods of preparation
US20040138401A1 (en) 2002-11-05 2004-07-15 Nina Bojkova High impact poly (urethane urea) polysulfides
US20070142604A1 (en) 2005-12-16 2007-06-21 Nina Bojkova Polyurethanes and sulfur-containing polyurethanes and methods of preparation
US20070238848A1 (en) 2001-11-16 2007-10-11 Bojkova Nina V High impact poly (urethane urea) polysulfides
US8017720B2 (en) 2005-12-16 2011-09-13 Ppg Industries Ohio, Inc. Sulfur-containing oligomers and high index polyurethanes prepared therefrom
US20070142602A1 (en) 2005-12-16 2007-06-21 Rukavina Thomas G Polyurethanes and sulfur-containing polyurethanes and methods of preparation
US20060241273A1 (en) 2001-11-16 2006-10-26 Bojkova Nina V High impact poly (urethane urea) polysulfides
US20070142603A1 (en) 2005-12-16 2007-06-21 Rukavina Thomas G Polyurethane(urea) and sulfur-containing polyurethane(urea) and methods of preparation
US20050282991A1 (en) 2001-11-16 2005-12-22 Bojkova Nina V High impact poly (urethane urea) polysulfides
US20030149217A1 (en) 2001-11-16 2003-08-07 Bojkova Nina V. High impact poly (urethane urea) polysulfides
CN1171924C (en) * 2002-11-05 2004-10-20 浙江大学 Method for preparing optical plastic of polythiocarbamic acid ether
US7009032B2 (en) 2002-12-20 2006-03-07 Ppg Industries Ohio, Inc. Sulfide-containing polythiols
WO2004099859A1 (en) * 2003-05-12 2004-11-18 Hopnic Laboratory Co., Ltd. Method for producing polarizing lens with high refractive index
US8604153B2 (en) 2004-09-01 2013-12-10 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070167600A1 (en) 2004-09-01 2007-07-19 Rukavina Thomas G Polyurethanes prepared from polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same
US20070167601A1 (en) 2004-09-01 2007-07-19 Rukavina Thomas G Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same
US20070225468A1 (en) 2004-09-01 2007-09-27 Rukavina Thomas G Polyurethanes prepared from polyester polyols and/or polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same
US20070149749A1 (en) 2004-09-01 2007-06-28 Rukavina Thomas G Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same
US20070173601A1 (en) 2004-09-01 2007-07-26 Rukavina Thomas G Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8178615B2 (en) 2004-09-01 2012-05-15 Ppg Industries Ohio, Inc Process for making polymers having nanostructures incorporated into the matrix of the polymer
US9464169B2 (en) 2004-09-01 2016-10-11 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8653220B2 (en) 2004-09-01 2014-02-18 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US8207286B2 (en) 2004-09-01 2012-06-26 Ppg Industries Ohio, Inc Methods for preparing polyurethanes
US8399559B2 (en) 2004-09-01 2013-03-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8734951B2 (en) 2004-09-01 2014-05-27 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US9598527B2 (en) 2004-09-01 2017-03-21 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US11149107B2 (en) 2004-09-01 2021-10-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20070148471A1 (en) 2004-09-01 2007-06-28 Rukavina Thomas G Impact resistant polyurethane and poly(ureaurethane) articles and methods of making the same
US8889815B2 (en) 2004-09-01 2014-11-18 Ppg Industries Ohio, Inc. Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom
US20090280329A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US20090280709A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US8399094B2 (en) 2004-09-01 2013-03-19 Ppg Industries Ohio, Inc. Multilayer laminated articles including polyurethane and/or poly(ureaurethane) layers and methods of making the same
US8859680B2 (en) 2004-09-01 2014-10-14 Ppg Industries Ohio, Inc Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US8927675B2 (en) 2004-09-01 2015-01-06 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US11008418B2 (en) 2004-09-01 2021-05-18 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8933166B2 (en) 2004-09-01 2015-01-13 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070251421A1 (en) 2004-09-01 2007-11-01 Rukavina Thomas G Powder coatings prepared from polyurethanes and poly(ureaurethane)s, coated articles and methods of making the same
US8349986B2 (en) 2004-09-01 2013-01-08 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20080118738A1 (en) 2006-11-17 2008-05-22 Boyer James L Microporous materials and multi-layer articles prepared therefrom
IN262320B (en) * 2005-12-16 2014-08-15
WO2007131149A1 (en) * 2006-05-05 2007-11-15 Ppg Industries Ohio, Inc. Thioether functional oligomeric polythiols and articles prepared therefrom
US8623989B1 (en) 2006-05-05 2014-01-07 PRC De Soto International, Inc. Polyurea/polythiourea coatings
US20110313084A1 (en) 2006-07-27 2011-12-22 Ppg Industries Ohio, Inc. Coating compositions comprising polyurea and graphite
US20090311504A1 (en) 2006-11-17 2009-12-17 Ppg Industries Ohio, Inc Microporous materials and multi-layer articles prepared therefrom
US20160024340A1 (en) 2006-12-14 2016-01-28 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20090171059A1 (en) 2008-01-02 2009-07-02 Gerkin Richard M Impact-Resistant Polyurethane
US9568643B2 (en) 2012-12-13 2017-02-14 Ppg Industries Ohio, Inc. Polyurethane urea-containing compositions and optical articles and methods for preparing them
KR20150117593A (en) * 2013-02-12 2015-10-20 폴리플렉스, 엘엘씨 Transparent polyurethanes
EP2801586B1 (en) * 2013-05-07 2016-04-13 Bruno Bock Chemische Fabrik GmbH & Co. KG Casting resin on a polythiourethane basis with high tensile strength and low specific weight
JP5997665B2 (en) 2013-06-19 2016-09-28 三井化学株式会社 Thermosetting polyurethane urea resin composition and molded article
WO2015046370A1 (en) * 2013-09-26 2015-04-02 三井化学株式会社 Eyewear material, eyewear frame and eyewear
CN104327237A (en) * 2014-10-10 2015-02-04 浙江海洋学院 Blue light-proof resin lens and preparation process thereof
ITBO20150179A1 (en) 2015-04-14 2016-10-14 Ali Group Srl Carpigiani MACHINE FOR MAKING ICE CREAM.
JP2017214488A (en) * 2016-05-31 2017-12-07 三井化学株式会社 Method for producing (thio)urethane-based molded body

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0406161A2 (en) * 1989-06-20 1991-01-02 Ciba-Geigy Ag Fluorine and/or silicone containing poly(alkylene-oxide)-block copolymers and contact lenses thereof
JPH08208794A (en) * 1995-02-03 1996-08-13 Mitsui Toatsu Chem Inc Production of sulfur-containing urethane plastic lens
CN101821309A (en) * 2007-10-15 2010-09-01 三井化学株式会社 Polyurethane resin
EP2227500A2 (en) * 2008-01-02 2010-09-15 Polyplexx, LLC Impact-resistant polyurethanes
US8372939B1 (en) * 2009-08-17 2013-02-12 Polyplexx, Llc Transparent polyurethanes
CN102918073A (en) * 2010-03-31 2013-02-06 陶氏环球技术有限责任公司 Polyurethane compositions having improved impact resistance and optical properties
CN104011103A (en) * 2011-11-18 2014-08-27 三井化学株式会社 Polymerizable composition, optical article obtained therefrom and method for the production of said optical article
CN105899563A (en) * 2013-12-10 2016-08-24 Ppg工业俄亥俄公司 Polyurethane urea-containing compositions and optical articles and methods for preparing them
WO2016006606A1 (en) * 2014-07-08 2016-01-14 三井化学株式会社 Polymerizable composition for optical material and use thereof
WO2016006605A1 (en) * 2014-07-08 2016-01-14 三井化学株式会社 Polymerizable composition for optical material, and application for same

Also Published As

Publication number Publication date
US20200140598A1 (en) 2020-05-07
EP3533817A4 (en) 2020-06-24
CN109715693A (en) 2019-05-03
WO2018079518A1 (en) 2018-05-03
JP6359231B1 (en) 2018-07-18
US11180602B2 (en) 2021-11-23
JP2018070865A (en) 2018-05-10
JPWO2018079518A1 (en) 2018-10-25
KR20190039259A (en) 2019-04-10
US10563003B2 (en) 2020-02-18
US20190127508A1 (en) 2019-05-02
EP3533817B1 (en) 2021-08-04
KR102172909B1 (en) 2020-11-02
EP3533817A1 (en) 2019-09-04

Similar Documents

Publication Publication Date Title
CN109715693B (en) Polymerizable composition for optical material, optical material obtained from the composition, and method for producing the same
CN109906240B (en) Polymerizable composition for optical material, and method for producing same
KR20080045215A (en) Polythiourethane-based polymerizable composition and optical resin obtained from the same
EP3168246B1 (en) Polymerizable composition for optical material, and application for same
JP2020181127A (en) Thiol-containing composition for optical material and polymerizable composition for optical material
JP7160649B2 (en) Polymerizable composition for optical material and optical material obtained from said composition
KR102445277B1 (en) A polymerizable composition for an optical material, a method for producing the polymerizable composition for an optical material, and a method for producing an optical article
US20230365737A1 (en) Iso(thio)cyanate compound, polymerizable composition for optical material, molded body, optical material, plastic lens, plastic polarizing lens, method for producing iso(thio)cyanate compound, method for producing polymerizable composition for optical material, method for producing optical material, and method for producing plastic polarizing lens
JP2020139096A (en) Polymerizable composition for optical material, optical material obtained from the composition and its production method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant